Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

• Cyclohexen-2-ol is a outstanding example of a connection that can be produced according to the invention. It is an important intermediate for e.g. the production of Nylon® or Dralon® (from cyclohexanone and ⁇ -caprolactam) and for the synthesis of fine chemicals.
• Cyclohexen-2-ol can be obtained by catalytic isomerization, i.e. H. free of others By-products or secondary products, cyclohexanone and by hydrogenation cyclohexanol are obtained (so-called KA oil, which is used as a preliminary stage e.g. for Nylon® and Dralon® Is used). In addition, phenol and catalytic dehydrogenation accessible by catalytic dehydration cyclohexadiene.
• Cyclohexen-2-ol has so far been obtained by the selective hydrogenation of phenol.
• This process consists of a large number of stages or sub-steps.
• phenol must first be produced from benzene, usually by the so-called cumene process, in which isopropylbenzene is obtained from benzene in a Friedel-Crafts alkylation.
• the disadvantage of this step is the high outlay, since this document cannot be carried out catalytically and correspondingly large amounts of, for example, iron salts are obtained from Friedel-Crafts alkylation, which must either be disposed of or worked up.
• This product is then rearranged into phenol and acetone with the help of oxygen.
• acetone is generally obtained as a by-product.
• the phenol obtained in this way is subjected to a selective hydrogenation which is stopped at the cyclohexen-2-ol stage.
• the process is therefore complex, provides large amounts of waste products that are difficult to recycle and, moreover, the by-product acetone, which is not desired in all cases.
• An overview is given, for example, by K. Weissermel and H.-J. Arpe in Industrial Organic Chemistry ", 4th edition, 1994, VCH Verlagsgesellschaft Weinheim, pp. 375 - 379.
• olefin metathesis could be regarded as a viable route for the synthesis of cyclohexen-2-ol and other ⁇ -substituted cycloolefins with this or larger ring size (a description of this type of reaction is given, for example, by M. Schuster, S. Blechert, Angew. Chem. 1997 , 109 , 2124 and S. Armstrong, J. Chem. Soc., Perkin Trans. 1, 1998 , 371).
• the dienes required as starting products can easily be made available by the so-called telomerization reaction or by other reaction routes known per se.
• the process according to the invention is based on starting materials which can preferably be obtained from a telomerization reaction (T. Prinz, W. Keim, B. Dr manen-Hölscher, Angew. Chem. 1996 , 108 , 1835; see also, for example, K. Kaneda, H. Kurosaki , M. Terasawa, T. Imanaka, S. Teranishi, J Org. Chem . 1981 , 46 , 2356; RM Manyik, KE Atkins, WE Walker, J. Chem. Soc. D. 1971 , 7, 330 and e.g.: K Kaneda, H. Kurosaki, M. Terasawa, T. Imanaka, S. Teranishi, J.
• the double bond in compound (II) can also be replaced by at least one R may be substituted.
• the nature of the substituent R is not essential for the invention; in principle, all residues common in organic chemistry can be used.
• the preferred alkyl groups R according to the invention are linear or branched C 1 to C 8 alkyl groups, particularly preferably linear C 1 to C 4 alkyl groups, and the aryl groups Y and R are preferably phenyl groups.
• the ring closure in the olefin metathesis reaction of the process according to the invention is brought about with a noble metal catalyst, preferably a ruthenium catalyst.
• a noble metal catalyst preferably a ruthenium catalyst.
• Particularly preferred catalysts in the process according to the invention are the ruthenium alkylidene compounds described in WO-A-93/20111, those by AW Stumpf, E. Saive, A. Deomceau and AF Noels in J. Chem. Soc., Chem. Commun . 1995 , 1127-1128 ruthenium-based catalyst systems or those described by P. Schwab, RH Grubbs and JW Ziller in J. Am . Chem. Soc . 1996 , 118 , 100 published catalyst systems related.
• Bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride is a particularly preferred catalyst.
• work is carried out continuously under a protective gas atmosphere, so that the catalyst system can be used over several cycles.
• the reaction time is variable and depends on the reaction temperature, the reaction pressure and the type and amount of the catalyst. Usually is the reaction time 0.01 to 30 hours, preferably 1 to 10 hours.
• the pressure to be used in the method according to the invention is not a critical parameter. Negative pressures of up to 0.1 bar and positive pressures of up to for example 100 bar can be used, but preferably 0.1 to 10 bar absolute Pressure, particularly preferably atmospheric pressure.
• the amount of catalyst in the process according to the invention is generally included 0.001 to 10 mol%, based on the compound of formula (I).
• reaction temperature is not a critical parameter. In general, the Reaction temperature by the boiling point of the solvent used or determined by the boiling points of the starting materials, unless the action of Pressure is counteracted.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Catalysts (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)
• Cephalosporin Compounds (AREA)
• Indole Compounds (AREA)

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• 1998
  • 1998-09-03 DE DE19840107A patent/DE19840107A1/de not_active Withdrawn
• 1999
  • 1999-08-24 ES ES99116199T patent/ES2210919T3/es not_active Expired - Lifetime
  • 1999-08-24 AT AT99116199T patent/ATE253028T1/de not_active IP Right Cessation
  • 1999-08-24 EP EP99116199A patent/EP0987239B1/fr not_active Expired - Lifetime
  • 1999-08-24 DE DE59907527T patent/DE59907527D1/de not_active Expired - Fee Related
  • 1999-08-27 JP JP11241369A patent/JP2000086550A/ja not_active Withdrawn
  • 1999-08-31 US US09/387,020 patent/US6303837B1/en not_active Expired - Fee Related
  • 1999-08-31 CA CA002281227A patent/CA2281227A1/fr not_active Abandoned

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